Method for extrusion of sheeting



Dec. l5, 1942.

F. R. coNKLlN Frm.

METHOD 0F EXTRUSION OF SHEETING Filed Sept. 27, 1939 2 Sheets-Sheet 1 l JQ 'J JQ- INVENTORS nldnnwwwnvwn S QN A YS Dec. 15, 1942.

F. R. coNKLlN ETAL METHOD OF EXTRUSION vOF SHEETING Filed Sept. 27, 1939 '2 Sheets-Sheet 2 52 FREDER/cK/Q CON/UN JaH/v Mean/1N INI/ENT ORS Patented Dec. 15, 1942 UNITED sTArEsf PATENT oEFIcE i i l u l j Y METnonfFoa nxligN or snEE'rmc. I

' Frederick n. 'Conklin and John s. Metallen,-

Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application September 27, 1939, Serial No. 296,834

` (ci. is-sv) jiclaims.

This invention relates to a process for the manufacture of sheeting from organic thermoplastic compositions; such as cellulose mixed organic acid ester compositions, thermoplastic resin composition, such as acetal resins, and in particular to'the manufacture of sheeting, suity able for use as the `interlayer in laminated glass,

from plasticlzed cellulose acetate butyrate compositions.

Various methods have heretofore been employed for making thermoplastic sheeting .for use in the manufacturevofflaminated glass. A very excellent process for making such sheeting fromV dellulose acetate' compositions is described in the copendingl application Serial No. 127,664, filed February25, 1937 nowy Patent 2,177,660. Another process for processing sheeting made'fromcellulose acetate compositions is described in the co-` these and other objects are attained by uniformly` extruding a hot homogeneously mixed thermoplastic composition thru a die orifice and .onto a pending application Serial No. 127,663, filed Feb- I ruary 25, 1937 now Patent` 2,177,659.

' In both of these, above mentioned applications one of the present'inventors, McLellan, is a joint inventor. In the :drst mentioned4 process, the

cellulose acetate sheet is extruded from a hotrevolving cold roll. The roll is maintainedat a relatively lower temperature than-the.extruded sheet. The cold roll serves to cool the sheet sufciently to eliminate substantially the undesiraf desired, by being passed thru a system of cooling rolls designed to cool both surfaces of the sheet and then may be immediately put to use or the These sheets were generally made from single i We have found that plastic sheeting containingy a base of a cellulose mixed organic acid ester such as cellulose acetate propionate, cellulose acetate butyrate, or others mounted hereinafter, particularly if plasticized with the s lvent plasticizersl such as diamyl phthala e, dibutyl phthalate lor others, presents a very diicult handling problem. Y Such hot sheeting tends to adhere to the guide rolls and to other surfaces over which it may pass. -It' alsomay stick together when woundup unless talc or other materials are employed to reduce the tackiness.

An object therefore of the present invention is anlmproved process of extruding organic'th'ercold sheet may be rolled up without'diiilculties due to adherence.

In accordance-with another feature of the invention, the composition may be extruded onto the revolving cold roll and then treated in a liqluid bath wherein the surface tackiness of the sheetis further eliminated. The sheetis then conducted thru a drying .cabinet to expel the liquid from the surface thereof, and is thenconducted thru a second drying or conditioning` from the following detailed description with refl erence to the attached drawings in which:

Fig, 1 is a plan view, chiefly in section, showing the elements of our improved apparatus for producing thermoplastic sheeting -up to the point where it is extruded onto the cold roll. t

Fig. 2 is an elevational view of one form of the apparatus showing the extrusion of the sheet onto the roll and its subsequentI progress to the windup roll.

Fig. 3 is an elevational view, part of the apparatusbeing in section, of an alternative form of be trimmed Referring to Fig. l, which represents the extrusion apparatus, up to the extrusion of the sheet onto the cold roll. there is shown a hopper I in which suitably mixed plastic granules, or the like, may be introduced. The hopper l0 is mounted above a screw conveyor assembly comprising a casing I2 having a cooling jacket `which is cooled with cold water, and a heating jacket I3 positioned in the walls'thereof, maintained by steam at a temperature of from 120 C. to 140 C., a chamber I4 positioned therein and a screw I rotatably mounted inthe chamber |4 and capable of being turned bymeans of pulley I6. The screw I5 has a plurality of slots |8 cut in its ights which cooperate with a plurality of lugs I9 to break up the plasticized granules and to cause the screw to feed continuously without any choking up.

Material introduced into the hopper |0 enters the chamber I4 where it is first cooled by the cooling jacket Il; the rotation of the screw l5 4will carry the material thru the heated section of the screw conveyor chamber during which it is heated and changes from 'a dough like stage to a thermoplastic mass.

,From the screw conveyor chamber the plastic material will be forced thru a preheater 20 which comprises a casing 2| having heating jackets 22 positioned in the walls thereof, a chamber 23 positioned within the casing 2|, and a heated core 24 positioned in the chamber 23. Heating fluids can be introduced into the hollow center `25 of device 24 thru inlet tube 26 and outlet tube 21. The core and the cylinder vare heated to temperatures of from 150 C. to 166 C. In this device the onowing plastic material is divided to a narrow width and is therefore uniformly preheated while passing between the walls of the casing and the internal core 24. The preheater and core are approximately 5 feet long. A

On leaving the preheater 20 the heated material will be forced thru inlet 28 into the Quimby pump 29 which is operated by a prime mover 3| thru drive shafts 30. The Quimby pump is heated by means of a heatvjacket (not shown) to temperature of 140 C. to 160 C. In this pump 29, the thermoplastic material is drawn in by rotating vanes (not shown) andv is thoroughly mixed, and then forced out of the top of thepump thru outlet 32 into the heated screw stuffer 33 thru inlet.32. This screw'stuffer 33 is heated by passing steam thru the heating jacket 34 contained in the stuier walls 35. A screw 36 is suitably mounted in the stuifer chamber 31 and is turned by suitable motive power thru its pulley 38 and shaft 39. The screw 36 may also be internally heated as is well known in the art. The temperature employed will be in the range of 140 C, to 160 C.

heat insulating jacket42 placed therearound. The screening device has acylindrical chamber 43 in which is placed in concentric: position a screen assembly 44. The screen assembly is mounted on circular end support members 45A and 46. Member 45 has an annular aperture 41 therein near the edge of the member while member 46 has a circular orifice 5| in its center portion. As will be clear from the drawings the plastic material is forced thru the annular aperl ture 41 and along the outside of the screen in the space 48 which soon lls. The continuous action of the stuffer screw 36 will then forceV the material in space 48 thru the screen into space 49. The lscreen will subdivide and homogenize the materialwhich will flow thru space 48 and out of orifice 5|. The screen assembly 44 may be made of a heavy mesh backing screen 52 and a fine mesh screen 53 placed thereover.

From the screening device theplastic flows into theextrusion die assembly 55. The construction of the d ieA assembly may be more clearly understood by Aalso referring, to Fig. 2 where there is shown an end elevation view in section of the die assembly and to Fig. 4 which is a side elevational view in section. The die.assembly 55 comprises a material conduit 56 into which the material is forced by the action of stuier screw 36. A plurality of slots 51 conduct the material to the extrusion die 58 thru a compacting chamber 59 and slot 6|. The conduit 56 is positioned in a steam heated chamber 62 which is formed by walls 63, 64, 65, and 66, and end walls 61 and 68. This is heated to 140 to 160 C. The die blocks 1I and 12 are positioned and suitably adjusted by bolts 13. As will be apparent, the width of the die orifice may be adjusted by these bolts. The temperature of the orifice may be suitably controlled by passinguds thru the passages 69. This temperature is maintained at 150 to 160 C. y

The plastic material which is forced out of the die 58 in the form of a sheet S will then contact the hollow cold roll 15 which is suitably cooled by means not shown. The 'roll -15 is mounted on support 11 thru its shafts 16. The temperature of the roll 15 is preferably maintained within 20 to 22 C. The roll 15 may ybe ad* justed to be relatively near or remote from the die orifice 58. Preferably it is maintained at a distance of 1to 3 inches below the die orifice.

The sheet S will tend to cling to the cold roll 15 and will pass around the. roll to the'take off roll 18 when it will be stripped from roll 15. The

sheet then passes betweenv drive rolls 8| and 82. From this point the sheet travels over-guide roll 83 and over the large cooling rolls 84 and 85 and4 which are mounted on support 86. The sheet then passes under guide roll 81 thru the'edge trimmer 88, thru the driving rolls 9| and 92 mounted on support 93, and to the windup roll 94 which is mounted on support 95.

The alternative method and apparatus for treating the extruded sheet is shown in Fig. 3,. The same extrusion die assembly 55 is employed as that shown and. described in connection with Fig. 2.

The sheet S is uniformly extruded from the die 58 onto the rotating cold roll 15. The sheet is removed from the roll 15 by roll |03 and enters a treating bath |04 contained in covered receptacle |05 which is positioned in heating cabinet |06. The sheet passes into the heating cabinet thru slot |01 and into the treating bath receptacle |05 thru slot |08 and is passed around the proximately l@ of theway down to the diester ate. di-z-etnyi buty1, db2-ethyl butyl saipatej dibutyl sebacate, diamyi sebacate, di-Z-ethyl guide roll |09 and leaves thru slot I||'. The sheet'then is drawn vertically thru the heating cabinet |06 and over guide roll ||2 and thence leaves the cabinet thru slot H3. The bath |04 contains a volatile solvent winch is subsequent- 5 ly expelled from the sheet when it leaves the bath by the heat in the cabinet |05. Heated air is -blown into the cabinet |06 by blower ||4 thru conduits, ||5, H0, ||1, and ||0 aswell as thru v air jets ||9, |2|, |22. The air leaves the cabil0 iet primarily thru outlet |23.

The sheet leaving the cabinet thru slot I3 passes between drive rolls |24 and |25 and thence into a conditioning cabinet |26 which is equipped with a conveyor to support the sheet. The conveyor passes around pulleys |28 and |29 andis constructed with wooden slats |3|. A 1steam` heating coil |32 is positioned in the cabinet to furnish the heat to remove any residual solvent remaining on the sheet. 'I'he sheet then passes 20 over guide roll |34 and thence thru'the cooling roll system( comprising rolls |35 and |33 which are mounted on support |31. The sheet then passes under guide roll |38,and thru the edge trimming device |39 thru driven rolls |4| and 25 |42 mounted on support |43 and is wound up on roll |44. j

It will be\ understood that the various moving parts of the apparatus are operatedin proper synchronism so that a continuous extrusion and treatment of the sheet is possible without subjecting the sheet to undue strains. 'l

While' the lprocess of the present invention can be employed to form thermoplastic sheeting from various materials and especially those which are tacky when extruded,.the invention is particularly suited for the production of cellulose acetate butyrate sheeting. Y

The preferred cellulose acetate butyrate em-A ployed as the base'of the composition may be de- 40 scribed as a stable organic acid ester of cellulose containing 30 to 55% butyryl having a viscosity of 5 to 75 seconds (1 part in 4 of acetone) and 1 to 2 free hydroxyls per 24 carbon atoms in the cellulose unit. 45

Such high butyryl cellulose esters may be prepared as described in Gardner Patent 2,113,301 of April" 5, 1938, or as described in the Malm and Kirton application referredl to below. The esters are preferably stabilized in accordance with the process disclosed and claimed by Malm and Kirton in their application Serial No. 254,492 iiled. February 3,` 1939.

It is desirable that the ester be one which has been stabilized in accordance with the Malm and Kirton process, or is one which has a stability which is equivalent to that of esters prepared ac- 'cording to that process (having a char point of at least 260 C.)

' An ester, which has been lfound to be particu- 6 larly satisfactory is one having a butyryl content of 35 to 38%, substantially the remainderV of the acyl being acetyl which hasbeen hydrolyzed ap-` plasticizers aresubstantially permanent intheir 70 -plasticizing e'ect within the usual range of atmospheric temperature (typified by 0 to 70 and 120 FJ. Various plasticizers may be employed for exfample such as dibutyl phthalate, ldiamyl phthal- 75 butylsebacate. The plasticizers may be emof cellulose ester.

If desired, other plasticizers may be mixed with the lplasticizers listed, to give a mixed plasticizer having suitable characteristics. or instance, a mixture of equal parts of dibutyl sebacate Vand triphenyl phosphate may be employed as the plasticizer with --good results. The plasticizer should be one which in the designated proportion in a sheet .025 thick of stable high butyryl cellulose acetate butyrate as deiined herein, such as the interlayer with glass of standard, quality, is capable of resisting the fall of a t lb. steel ball i'roma height of 15 feet.

While various methods of mixing the acetate butyrate and plasticizer may be employed we have found the two iollowingunethods quite suitable to produce a uniformly plasticized composition.

The mixing operation is .carried out in a jacketedsigma blade type mixer of the type described in the Palmer Patent 2,150,939 of March 21, 1939.

The cellulose acetate butyrate and the diamyl phthalate are cooled to --room temperature and are added to the mixer. 'I'hey are thoroughly mixed at a temperature of 15 to 20 C. this temperature being maintained by circulating cold water throughthe mixer jacket. The flow of water is thenstopped and the mixer is intermittently agitated until the temperature of the mix rises to room temperature. Hot water is then circulated through the mixer jacket and the mixer is intermittently operated. cooled to room temperature by passing cold water thru the jacket with intermittent agitation.V

Example H Parts Cellulose acetate butyrate v 100 Dibutyl phthalate--- 771/2 The mixing of this compositionis conducted in the same 4type of mixer as mentioned above in Example I. The acetate butyrate is added-to the mixer at room temperature and water at a compositions we employ since we have found that the presence of residual solvents in the composition results in blowinsf in the laminated glass it being substantially impossible to remove all of the included solvents. However, the instant process isnot limited to the.v extrusion of non-volatilesolvent. containing "materials even lthougha superior'sheet is produced from such compositions. .Y

The composition obtained by either of these mixing processes is in a dough stage at the end of the mixing operation. The homogeneously The mix is nally Preferably no volatile mixed dough is then broken up into small pieces or granulated and these pieces or granules may then be fed into the apparatus described above. As previouslyl suggested various thermoplastic resin base compositions may also be employed according to our improved process to form thermoplastic sheeting for' laminated glass. We have found that thermoplastic resins which may be broadly identified as polyvinyl acetal resins, or polyvinyl acetaldehyde acetal resins, or mixed polyvinyl acetal resins, or polyvinyl maleyl estei lactone resins, are particularly adaptible as base resin materials from which sheeting suitable foi use in laminatedY glass can be made.

An example of a suitable polyvinyl acetal resin is that known by the trade name Vinylite X," which rwe understand to be a polyvinyl butyi'aldehyde acetal resin containing a hydroxyl group content equivalent to about 20% by weight, ot polyvinyl alcohol.

An example of a polyvinyl acetal resin is that known by the trade name Formalvar which appears to be a polyvinyl formaldehyde acetaldehyde.

The resin known by the trade name Alvar is representative of a polyvinyl acetaldeliyde acetal resin suitable for use in our process. An example of a polyvinyl maleyl ester lactone resin is butyl maleate vinyl acetate.

In addition to these resins other thermoplastic resins which do not have too high softening points may be employed.

These resins may be plasticized with the dialkyl phthalate plasticizers, such as dimethyl, diethyl, dipropyl and diamyl phthalates, alkyl'sebacates, such as dibutyl sebacate. ethyl phthalate, dimethyl succinate, dimethyl and dibutyl maleate may also be employed.

Typical examples of plasticized resin compositions are the following:

Example III These formulas can be mixed in a sigma blade mixer, the temperature being kept at room temperature or below during the mixing as described previously. The extruding temperatures will -be about 130 to 140 C.

Our process for making thermoplastic sheeting will be more clearly understood from the fol-V lowing description of forming a sheet from the cellulose acetate butyrate composition disclosed in Example I.

Granules of the composition are, regularly introduced into hopper I of the apparatus by an automatic feeding device (not shown). From the hopper |0 the granules flow into the cold end of the screw stuffer froml which they are grad ually transferred by the screw l5 thru the stuier chamber, |4. During this transfer the granules are changed by Ithe heat and pressure in the stuler to a thermoplastic mass. Thel granules are heated in the stuffer from 120` to 140' C. The temperature of the mass'is raised in the preheater to about 140 to 160 C. In the preheater 20 the onflowing plastic is forced by the action of screw l5 around the heated core 24 Tripropionimmethoxy y and is, therefore, exposed in thin cross section to heat from both the jacket 22 and core 24.

The continued action of screw I5 forces the plastic thru. the preheater 20 and into the Quimby pump 29 which is also maintained at a temperature of 140 to 160 C. The vigorous mixing action of this pump assures a very homogeneous composition. The pump 29 forces the plastic into the screw stufer 33 which is also maintained at a temperature of 140 to 160 .C.

The screw stuler forces the plastic into the screening device y4| where it is further com-` minuted and any foreign matter separated. The continuous action of the screw then forces the plastic into the extrusion die assembly thru orifice 5|, (see Figs. 2 and 3). The die assembly 55 is maintained at a temperature of from 140 to 160 C. The plastic material, referring to Fig. 2, is forced out of conduit 56 thru the pluralityof slots 51 into the compacting chamber 59; it then flows thru slot4 6| to the extrusion orifice 58 from which it is continuously extruded in the form of a thin sheet S.

The sheet S is immediately picked up on the cold roll 15 which is at such a short distance from the orifice that the weight of the length of the extruded sheet between the orifice and cold roll is less than that which would tend .to stretch the sheet.

The cold roll 15 which is maintained at about 20 C. tends to chill the surface of the sheet and greatly reduces its adherence. tend to stay on the roll 15 and be carried around to roll 18 at which point it is sufficiently cooled wound on roll 94.

to be easily stripped off roll 15. "Roll 18 is a free turning roll and the sheet is drawn there-g over by the action of drive rolls 8| and 82 which are driven at a rate less than that which will tend to stretch the sheet. From the drive roll the sheet is passed over the guide roll 83 and then over cold rolls 84 and 85 which cool opposite sides of the sheet. This final cooling will assure that the temperature of the sheet is below the adherence point. The sheet is then trimmed to a desired width by trimmer 88 and Drive rolls 9| and 92 serve to draw the sheet thru the trimmer 88.

Referring to Fig, 3 the alternative -method of treating the extruded sheet will be described.

The sheet S is extruded onto the roll 15 as heretofore described Where it is chilled and removed from the roll 15 by roll |03. It is then drawn into the solvent bath |04 when it passes around freely turning roll |08. The action of the solvent on the cellulose acetate butyrate sheeting produces a White and somewhat roughened sheet which is not tacky at normal temperatures. When, however, this sheeting is pressed between glass plates in the laminf ting operation, the sheeting becomes highly transparent. Neither the haze value or the result However, it will i 1. The method of forming athermoplastic sheet exhibits substantial adherence to the surface,

of the break tests are affected by the solvent treatment.

As the sheet reaches the bottom of the bath, A it is very soft and subject to undesirable roughthe Sheet. heating the Sheet t remove any solening and consequently the guide roll |09 must 5 Vent remaining thereon. and furthercooilng the be mounted to turn freely so that, n0 slippage sheet to a point below which it exhibits substanof the sheet will occur. tiel adherence tendencies.

As the sheet emerges from the bath |04 its 2' The method 0f fOllning atheimopiastle Sheet surface is very sofi; due to the action of the fromaplasticized cellulose acetate butyrate comsolvent and in order to prevent wrinkling, it is 10 POSitiOn Which iS Particularly tacky and adherent desirable that the wet sheet touch nothing until the preliminary drying has been completed. 'I'he further lowering the adherence of the sheet by the hot composition through a die to form a. sheet, sheet is therefore drawn vertically from the bath permitting the forming Sheet t0 Contact freely a over the supporting` roll |I2 in heating cabinet iilOVlng Cooling Surface and adhere thefetO, inOV-.. |06, which may be eight to ten feet above the 1118 Said Sillleee el? e rate Substantially equal t0 beth. This distance wiii vary with dinerent types the extrusion rete, whereby substantially no tenof sheeting and solvent; baths, sion is exerted on the sheet, stripping the sheet The preferred gewent for use in the bath is from the surlace when it lhas been cooled to a methanol, however, the following solvents and P0111t 'below Which it eXhibltS Substantial adhersolvent, combinations may be emp10yed 20 ence fr0 'Une Surface, further lOWeI'ing the adherence of the sheet by passing it through a bath forming sheet to contact freely a moving cooling v suriace and adhere thereto, moving said surface Het air from pipes H5, H6, l1, H3, H9, izl at a rate substantially equal to the extrusion rate, and |22 will drive off the major portion of thev Wiflelell? Substantially n0 tension iS exerted on solvent contained on the sheet and the solvent me Sheet, stripping Athe Sheet from the surface vapors will be removed through vent |23 by a When it has been Cooled t0 e Peint below which it suction une, not Shown exhibits substantial adherence to the suriace, The sheet leaves the cabinet thru opening 3 further lowering the adherence 0f the Sheet. by and passes thru drive rolls |24 and |25 which serve passing it through a bath eontaining a solvent to draw the sheet thru the cabinet |00. The sheet 4;, which will attack the surface of the sheet," heatis conducted on the endless conveyor |21 thru the i118 the Sheet t0 VaDOriZe the Solvent from the surheated conditioning cabinet |26. This conditionface 0f t311e Sheet eenaueiing the Sheet While it ing cabinet may be 30 feet long. The temperature iS Supported. Without sumitaxitialI tension being exis maintained between to 60 C. by the heating erted thereon through la. heated conditioning unit |32, and this treatment will remove any re- 5o flileinbeifV Wheeirlfilnif` solvent is residual solvent traces remaining on the sheet. moved. cooling the'sheet. From the conditioner |26 the sheet is passed over 4l ,The "ethocl of forming'f Acooling rolls |35 and |36, thru the rotary trimf mers |39, draw rolls |4| and |42 and is wound up i onspool |44. "'65 adherent hot. bien' 'i' mprises unilormly By employing these methods, we have been Suo- )e1-mf iShe' hot 'com cessful in producing sheets of the above described "forma materials without the undesirable features heretofore experienced when usingv processes fof prior art.

Water -15 y stripping heet from f f from a thermoplastic composition which .is par.-` been ycool tos'a ,pointlbelow which it exhibits ticularly tacky and adherent when hot, which 'ellbstantial erencetothe surface, further lowcomprises uniformly extruding the hot composieringheedherence of 'the sheet by passing it tion through a die to form a sheet, permitting the through. a bath containing a solvent for the sheet, formed sheet to contact freely a meting cooling heating the Sheet to remove any solvent remainsurface and adhere thereto, moving Asaid surface lng thereon, and further cooling the sheet to a. at a rate substantially equal to the extrusion rate Point below which it exhibits substantial adherwhereby substantially no tension is exertedl on ence tendencies. the sheet, stripping the sheet from the surface when it has been cooled toa point below which it What we claim is:

.FREDERICK R. CONKLIN. JOHN S. MCLELLAN passing it through a bath containing a solvent for when hot, which comprises uniformly extruding 

